CN104334707A - Laundry detergent compositions comprising polyalkoxylated polyethyleneimine - Google Patents

Laundry detergent compositions comprising polyalkoxylated polyethyleneimine Download PDF

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CN104334707A
CN104334707A CN201380025584.1A CN201380025584A CN104334707A CN 104334707 A CN104334707 A CN 104334707A CN 201380025584 A CN201380025584 A CN 201380025584A CN 104334707 A CN104334707 A CN 104334707A
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CN104334707B (en
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S·N·巴切洛尔
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Unilever IP Holdings BV
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Unilever NV
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    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/37—Polymers
    • C11D3/3703—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • C11D3/3723—Polyamines or polyalkyleneimines

Abstract

A laundry detergent composition containing 5 to 30 wt% detersive surfactant selected from non-ionic and anionic surfactant and 0.05 to 4 wt% of polyalkoxylated polyethylene imine polymer where the polyalkoxyl chains are directly linked to the nitrogens in the PEI and each chain has a terminal group with molecular weight less than 100 and wherein the polymer is a PEI which has a molar ratio of polyalkoxyl chains, including the terminal group, to PEI of less than or equal to 3 resulting in 3 or fewer, preferably 2 or fewer, most preferably 1 nitrogen(s) bound to polyalkoxyl chains and wherein the PEI has a Mw of at least 500, preferably 1000 to 2000, more preferably less than 1500 and even about 1300.

Description

Comprise the laundry detergent composition that poly-alkoxylation is polyethylene imine based
Technical field
The present invention relates to laundry detergent composition, it comprises the polyethylene imine based anti-redeposition polymkeric substance (ARP) of alkoxylate and detergent surfactant, especially anionic and nonionic detergent tensio-active agent.
Background technology
In CA 1210009, known ethoxylation PEI (PEI=is polyethylene imine based) is anti-redeposition polymkeric substance.All primary and secondary amino is fully by EO 20pEI (600) the 20EO material that poly-alkoxylation replaces is not the good ARP for detergent for washing clothes.These alkoxylate PEI are usually by oxyethane, and/or propylene oxide, formed with the PEI direct reaction described in such as CA 1210009.
EP 2050792 (DIC company) discloses the preparation that PEI adds tosylation PEG monomethyl ether, and it is the intermediate in the preparation of PEG-PEI-epoxy resin structural.This preparation is repeated in EP2147733.
JP 2007/099929 (Dainippon Ink & Chem.) also discloses tosylation PEG monomethyl ether and adds PEI to, then adds styrene monomer.
S.Xu etc. (Macromolecular Bioscience the 7th volume 968-74 page, 2007) use tosylation monomethyl ether PEG to prepare the PEI of aryl replacement as intermediate, and it has the PEG base being connected to benzyl rings.
In the above documents, the mol ratio of mPEG to PEI of use is at least 3: 1, and it should give average at least 3 poly-oxyalkyl chains being connected to each PEI.
Zhang & Lonnie (Chinese J.Chem., the 21st page of 460-5 page, 2003) discusses preparation and their clay dispersibility of PEI-PEO segmented copolymer.Described polymkeric substance is the triblock polymer that the PEG (dimesyl (dimesyl)) modified by divalence is formed.This forms PEO and is cross-linked between two kinds of PEI bases.Crosslinked PEI like this due to its lower weight efficiency be undesirable.
The preparation comprising non-ionic type is widely used for laundry, especially for being suitable for low brewed dose of button fly front automatic washing machine.
PEI tends to dirt deposits on nylon elastic fiber base fabric.EPEI can not meet with the same nylon elastic fiber negative impact as PEI, and is therefore widely used in laundry composition.But, need improvement EPEI to solve in load of typically doing washing as the performance of soil suspending polymer: the redeposition problem on the gamut fabric found in cotton, polyester-cotton blend, polyester and nylon elastic fiber.
invention summary
According to a first aspect of the invention, a kind of laundry detergent composition is provided, it comprises the detergent surfactant being selected from non-ionic type and aniorfic surfactant of 5 to 30wt%, and 0.05 arrives 4wt%'s, the preferably poly-alkoxylation polyethyleneimine polymers of 0.1 to 2wt%, wherein said polymkeric substance is that poly-oxyalkyl chain is less than or equal to the PEI of 3 relative to the mol ratio of PEI, it causes 3 or less nitrogen-atoms, preferably 2 or less nitrogen-atoms, most preferably 1 nitrogen-atoms is attached to poly-oxyalkyl chain, wherein PEI has at least 500, preferably 1000 to 2000, more preferably less than 1500, the Mw of even about 1300.
Mw is weight-average molecular weight.Described molecular weight measures preferably by using the dynamic light scattering of Zetasizer Nano (Malvern).
Suitably when each PEI has more than a poly-oxyalkyl chain, each PEI nitrogen-atoms only has a poly-oxyalkyl chain.
Preferably the mark of (wt% non-ionic type)/(wt% aniorfic surfactant) is from 0.6 to 2.0, preferably from 0.90 to 1.2.
Same according to the present invention, a kind of washing methods is provided, wherein will be diluted to 0.3 according to the composition of first aspect to 1g/L tensio-active agent, and 5 to 150ppm, preferably 10 to 80ppm according to the level of the polymkeric substance of first aspect, and uses it for laundering of textile fabrics.
Every bar gathers oxyalkyl chain and preferably sets up group from oxyethyl group and/or propoxy-.It is most preferably polyethoxye chain.Preferably described poly-oxyalkyl chain comprises 5 to 50, more preferably 8 to 20, most preferably 10 to 14 alkoxy repeat units.Chain can be OH or alkyl end envelope, and preferably methyl end seals.Gather the bonding of oxyalkyl chain and PEI for the ease of end envelope, described chain is preferably provided with reactive group to be connected to PEI at end.Suitable reactive group can be selected from epoxide, alkene, sulfo group oxygen ethylsulfonyl reactive group (-SO 2cH 2cH 2oSO 3na), heterocyclic reactive radicals and leavings group such as tosyl group.Described heterocyclic reactive radicals preferably in conjunction with the nitrogenous aromatic ring of halogen or ammonium, itself and NH 2or NH radical reaction forms covalent linkage.In order to avoid crosslinking reaction, preferably described preformed oxyalkyl chain only comprises 1 reactive group, another-end of the chain alkyl end envelope typically.
The exemplary construction of described poly-alkoxylation PEI polymkeric substance is structure (I), and wherein alkoxylate is ethoxylation, and end end group is methyl and EO number of unit is 13:
detailed Description Of The Invention
Described detergent composition can adopt any suitable form.Such as they can be powder, sheet, liquid or gel, and in the case of a liquid, they can be included in water miscible capsule easily to use.Because poly-alkoxylation PEI ARP material and typical case in liquid washing agent exist the consistency of composition, preferred composition is liquid.
tensio-active agent
Tensio-active agent helps from textile materials removing dirt, and helps the dirt of the removing maintaining solution or form of suspension in washings.The blend of anionic and nonionic surface active agent is preferred composition feature.The amount of aniorfic surfactant is preferably at least 5wt%, more preferably at least 10wt%.
anionic
Preferred aniorfic surfactant is alkylsulfonate, especially alkylbenzene sulfonate, particularly has C 8-C 15the linear alkylbenzene sulfonate of alkyl chain length.Gegenion for aniorfic surfactant can be basic metal, typically sodium, or other gegenions such as can use MEA, TEA or ammonium.
Suitable linear alkyl sulfonate surfactant comprises and has 8 to 15, more preferably the Detal LAS of long alkyl chains of 12 to 14.
The alkyl polyethoxylate sulfates aniorfic surfactant that described composition comprises formula (II) is desirable further:
RO(C 2H 4O) xSO 3 -M +(II)
Wherein R has from 10 to 22 carbon atoms, saturated or undersaturated alkyl chain, and M is positively charged ion, and it makes described compound be water miscible, especially basic metal, the ammonium cation of ammonium or replacement, and x is on average from 1 to 15.
Preferably R has the alkyl chain from 12 to 16 carbon atoms, M be sodium and x on average from 1 to 3, preferably x is 3; This is aniorfic surfactant Zetesol NL (SLES).It is the sodium salt of lauryl ether sulfonic acid, wherein mainly C 12every mole, lauryl alkyl carrys out ethoxylation with the oxyethane of average 3 moles.
non-ionic type
Nonionic surface active agent comprises primary and secondary alcohol ethoxylate, particularly every mol of alcohol C of the oxyethane ethoxylation of average 1 to 20 moles 8-C 20fatty alcohol, and more especially every mol of alcohol C of the oxyethane ethoxylation of average 1 to 10 moles 10-C 15primary and secondary fatty alcohol.Non-ethoxylated nonionic tensio-active agent comprises alkyl poly glucoside, glycerol monoethers and polyhydroxy amides (glucamide).The mixture of nonionic surface active agent can be used.When being included in wherein; described composition comprises 0.1 to 20wt%, preferably 1wt% to 15wt%, more preferably the nonionic surface active agent of 5 to 15wt%; such as alcohol ethoxylate; nonyl phenol ethoxylate, alkyl poly glucoside, alkyl dimethyl amine oxide; the fatty monoethanol amide of ethoxylation; fatty monoethanol amide, polyhydroxy alkyl fatty acid acid amides, or the N-acyl N-alkyl derivatives of glycosamine (" glucamide class ").
Operable nonionic surface active agent comprises primary and secondary alcohol ethoxylate, especially every mol of alcohol C of the oxyethane ethoxylation of average 1 to 35 moles 8-C 20fatty alcohol, and more particularly every mol of alcohol C of the oxyethane ethoxylation of average 1 to 10 moles 10-C 15primary and secondary fatty alcohol.
amine oxide
Described composition can comprise the amine oxide of the formula (III) being up to 10wt%:
R 1N(O)(CH 2R 2) 2(III)
Wherein R 1long-chain moiety, each CH 2r 2it is short chain moieties.R 2preferably be selected from hydrogen, methyl and-CH 2oH.Generally speaking, R 1be main chain (primary) or branched hydrocarbyl moieties, it can be saturated or undersaturated, preferably R 1it is main chain moieties.R 1have from about 8 to the hydrocarbyl portion of about 18 chain lengths.
Preferred amine oxide has R 1c 8-C 18alkyl, and R 2h.These amine oxides are by C 12-14alkyl dimethyl amine oxide, cetyl dimethyl amine oxide, octadecyl amine oxide example.
Preferred amine oxide material is lauryl dimethyl amine oxide, also known as dimethyl dodecyl amine oxide or DDAO.Such amine oxide material can from Huntsman with trade(brand)name oB is purchased.
Be applicable to amine oxide herein to obtain from Akzo Chemie and Ethyl company equally.See editor and the Kirk-Othmer survey article of the McCutcheon for the amine oxide manufacturers substituted.
And in the preferred embodiment, R 2h, likely R 2slightly large than H.Specifically, R 2can be CH 2oH, such as: two (2-hydroxyethyl) amine oxide of hexadecyl, two (2-hydroxyethyl) amine oxide of ox ester, two (2-hydroxyethyl) amine oxide of stearyl and two (2-hydroxyethyl) amine oxide of oil base.
Preferred amine oxide has formula (IV):
O --N +(Me) 2R 1(IV)
Wherein R 1c 12-16alkyl, preferably C 12-14alkyl; Me is methyl group.
amphoteric ion type
Preferred zwitter-ion shaped material is can from Huntsman with title the carbobetaine (carbobetaine) that BB is purchased.Betaines and/or amine oxide, improve dirt particles detergency in the composition.
other tensio-active agent
Except preferred LAS, SLES, outside non-ionic type and amine oxide/carbobetaine type, other tensio-active agent can be added in the mixture of detergent surfactant.But cationic surfactant is preferably substantially non-existent.
Although preferably less, some alkyl sulfate surfactants (PAS) can be used, especially unethoxylated C 12-15primary and secondary alkyl-sulphate.The especially preferred material that can be purchased from BASF is Sulfopon 1214G.
polymkeric substance
polyester soil release polymers
Described composition can comprise the soil release polymers of 0.5wt% or more, and it is effective to polyester textile.This polymer Typical ground has the fabric validity mid-block (midblock) formed by the repeating unit of the sub-propyl ester of terephthalic acid, end-blocks with the polyalkylene oxide that one or two end seals, typically has the PEG 750 to 2000 of methyl blocking.
other polymer type
Except polyester soil release polymers, can dye transfer inhibiting polymers be used, and cotton soil release polymers, especially those are based on the cellulosic material of modification.
hydrotrote
Hydrotrote is a kind of solvent, and it is neither water, tensio-active agent that neither be conventional, and described hydrotrote increases described tensio-active agent and the solvency action of other components in waterborne liquid to make its isotropy.In suitable hydrotrote, can preferably should be mentioned that: MPG (MPG), glycerine, sodium cumene sulfonate, ethanol, other glycol, such as dipropylene glycol, diether and urea.
enzyme
Preferably, at least one or multiple enzyme may reside in described combination species.Preferably at least two kinds, more preferably at least three kinds of dissimilar enzymes combinationally use.Preferred enzyme mixture is selected from: lipase, Phospholipid hydrolase, proteinase, at, amylase, cellulase, peroxidase/oxydase, pectate lyase, and mannase.
Any enzyme be present in described composition can use conventional stablizer stabilization; such as polyvalent alcohol is as propylene glycol or glycerine; sugar or sugar alcohol; lactic acid; boric acid, or boric acid derivatives, as aromatic boric acid ester; or phenyl boronic acid derivative is as 4-formyl phenylboronic acid, and described composition can as preparing of describing in such as WO 92/19709 and WO 92/19708.Or, or additionally, described enzyme can be protected by encapsulating.
When comprising lipase, lignin compound may be used for described composition.Preferably described lignin compound comprises lignin polymers, and more preferably it is modified lignin polymer.As used herein, modified lignin polymer is a kind of xylogen, and it has stood chemical reaction and chemical part is covalently attached to described xylogen.The chemical part connected preferably replaces at random.
fluorescent agent
It is favourable for comprising fluorescent agent in the composition.Usually, these fluorescent agents provide with their alkali metal salt and use, such as sodium salt.For the total amount of one or more fluorescent agents in described composition usually from 0.005 to 2wt%, more preferably 0.01 to 0.5wt%.
Preferred fluorescent agent classification is: distyryl biphenyl compound, as Tinopal (trade mark) CBS-X, diamines Stilbene disulfonic acid compound, Xtra as pure in Tinopal DMS, Tinopal 5BMGX, with Blankophor (trade mark) HRH, and pyrazoline compound, as Blankophor SN.
Preferred fluorescent agent is: 2 (4-styryl-3-sulfo group phenyl)-2H-naphthols [1,2-d] 1-Sodium-1,2,4-Triazole, 4,4 '-bis-{ [(4-anilino-6-(N methyl-N-2 hydroxyethyl) amino 1,3,5-triazine-2-base)] amino Stilbene-2-2 ' disulfonate, 4,4 '-bis-{ [(4-anilino 6-morpholino-1,3,5-triazine-2-base)] amino Stilbene-2-2 ' disulfonate, and 4,4 '-bis-(2-sulfostyryl) biphenyl disodium.
bleach catalysts
Composition can comprise the bleach systems of effective weight.Such system does not typically utilize conventional percarbonate and activator of bleaching agent approach.Air bleaching agent catalyst system is preferred.Suitable complex compound and organic molecule (part) precursor for the formation of complex compound be that those skilled in the art are obtainable, such as, from WO 98/39098; WO 98/39406, WO 97/48787, WO 00/29537; WO 0052124, and WO00/60045, it is incorporated to herein as a reference.The example of preferred catalyzer is the transition metal complex of MeN4Py part (two (pyridine-2-the base)-1-ethylamine of two (pyridine-2-base-methyl)-1-, the 1-of N, N-).WO02/48301 describes suitable bispidon catalystic material and their effect.Described bleach catalysts can be encapsulated to reduce at memory period and other the interaction of component of described liquid.
Also optical white can be used." optical white " is the chemical species of the bleaching species class of any forming reactions when being exposed to sunlight, and is not preferably for good and all consume in described reaction.Preferred optical white comprises singlet oxygen optical white and radiant light SYNTHETIC OPTICAL WHITNER.Suitable singlet oxygen optical white can be selected from water miscible phthalocyanine compound, especially metallized phthalocyanine compound, and wherein metal is Zn or Al-Z1, and wherein Z1 is halogenide, vitriol, nitrate, carboxylate salt, alkoxide or hydroxide ion.Preferably described phthalocyanine has 1-4 the SO be covalently bound on it 3x group, wherein X is basic metal or ammonium ion.Such compound is described in WO2005/014769 (Ciba).
When it is present, described bleach catalysts is that preferably the content of about 0.001 to about 5wt% is introduced typically with about 0.0001 to about 10wt%.
perfume compound
Described composition comprises one or more fragrance components usually.The perfume compound without oil and encapsulating can be used, and composition thereof.
Guarantee that perfume compound be the particularly preferred mode of effective use is the perfume compound using encapsulating.The perfume compound of encapsulating is used to reduce the amount of the perfume compound steam produced by described composition before its dilution.This when increasing described fragrance concentration in case allow the amount of perfume compound in each washing remain on one reasonably high-content time be important.
Even more preferably, perfume compound is not only encapsulated, and the perfume compound of encapsulating provides together with deposition aid so that the efficiency increasing perfume compound deposition and be retained on fabric.Described deposition aid is preferably by covalent linkage, and tangling (entanglement) or adsorbing by force is connected to described encapsulation object.
other optional members
Described composition can comprise one or more other composition.Such composition comprises viscosity modifier, suds booster, sanitas (such as sterilant), pH buffer reagent, polyelectrolyte, sanforzing agent, crease-resistant reagent, antioxidant, sun-screening agent, inhibitor, pendency imparting agent (drape imparting agent), static inhibitor and pressing auxiliary agent (ironing aid).Described composition can also contain toner, pearling agent and/or opalizer, and covers dyestuff.
cover dyestuff
Cover the performance that dyestuff can be used for improving described composition.Preferred dyestuff is purple or blueness.It is believed that the deposition on fabric that these cover the low levels of dyestuff covers the jaundice of fabric.Another advantage of covering dyestuff is that they can be used for covering any yellow tone of described composition itself.The example covering dyestuff is alkoxylate thiophene dyestuff, acid violet 50, directly purple 35, directly purple 99, direct purple 9, and solvent violet 13,63 ,DIS,PER,SE ,Vio,let, 63 28, EX-SF DISPERSE BLUE EX-SF 300 165.
Cover dyestuff when may be used for there is not fluorescent agent, but especially preferred use together with fluorescent agent covers dyestuff, such as, in order to reduce the jaundice because the chemical transformation on the fluorescent agent of absorption causes.
washing assistant and sequestrant
Described detergent composition also optionally can comprise organic detergent builders or the sequestrant material of relative low levels.Example comprises basic metal, Citrate trianion, succinate, malonate, carboxymethyl succinates, carboxylate salt, polycarboxylate and poly-ethanoyl carboxylate salt.Concrete example comprises the sodium of oxygen base disuccinic acid, mellitic acid, benzene poly carboxylic acid and citric acid, potassium and lithium salts.Other example is the DEQUEST sold by Monsanto tM, organically phosphonic acid ester sequestering agent, and alkane hydroxyl phosphonic acid ester.
Other suitable organic washing assistant comprises known polymkeric substance and the multipolymer with the more high molecular of washing assistant performance.Such as, such material comprises suitable polyacrylic acid, polymaleic acid and poly propenoic acid maleic acid and their salt, and the name of such as being sold by BASF is called SOKALAN tMthose.
If used, organic builder material can account for about 0.5% of composition to 20wt%, preferably 1wt% to 10wt%.Described preferred washing assistant content is the 10wt% being less than composition, and is preferably less than 5wt%.Preferred sequestrant is HEDP (1-hydroxy ethylidene base-1,1 ,-bisphosphate), such as, sell as Dequest 2010.But other suitable less preferably provide inferior clean result be 2066 (diethylenetriamine five (methylene phosphonic acid or seven sodium DTPMP).
buffer reagent
The existence of some buffer reagents is preferred for pH regulator; Preferred buffer reagent is MEA, and TEA.If existed, they are preferably used for described composition with the content of 1 to 15wt%.
external structurant
Described composition can have by utilize formed within described composition structured network-kind or the rheological property of multiple material modification.Suitable structurising agent comprises hydrogenated castor oil, the Mierocrystalline cellulose of primitive fiber and natural based structures agent, as citrus pulp fiber.Citrus pulp fiber is especially preferred, if described composition comprises lipase especially.
visible indicia
Described composition can comprise the visible indicia of solid material, and it is insoluble to described composition.Preferably they are for combining to guarantee that they maintain with form of suspension with the structurising agent of outside.Preferred visible indicia be formed by polymeric film with the laminar mark that may comprise functional composition, if described functional composition be exposed to alkalescence liquid time may not stablize as such.Enzyme and bleach catalysts are the examples of such composition.Also can be the perfume compound of perfume compound, especially microencapsulation.
The present invention will describe with further reference to following non-limiting examples now.
Embodiment
macroscopic single crystal
step (a): the tosylation of the polyoxyethylene glycol of methyl blocking
At 0 to 5 DEG C, the PEG methyl ether under the stirring that 45min toluene sulfonyl chloride is added in methylene dichloride and triethylamine mixture.Then allow this mixture to be heated to envrionment temperature, and at room temperature stir 16 hours.After this, all toluene sulfonyl chlorides consume substantially, as what judged by tlc.Reaction creates the suspension (192g) of tosylation PEG.
step (b): polyethylene imine based " polyethoxylated "
Tosylation PEG suspension in step (a) mixes for 10.5 times at pH with polyethylene imine based (Mw=1300) solution of 50wt%.Tosylation PEG is 1: 1 relative to polyethylene imine based mol ratio.At room temperature, stir described mixture overnight (16 hours), complete the formation of tosic acid afterwards, as by TLC detect, then with concentrated hydrochloric acid regulate pH to 7.0 and bottling.Come to synthesize described in repetition relative to polyethylene imine based mol ratio with different tosylation PEG, to provide a series of polymkeric substance as described in detail in table 1.The comparative example that P10 and P30 is labeled, because the alkoxylate that they are similar to prior art is polyethylene imine based.
table 1
washing test
Table 2 gives the basic laundry detergent composition for washing test.
table 2
W% (solid)
NaLAS 4.9
NI(7EO) 7.3
SLES (3EO) 2.4
Alkyl betaine 0.9
1,2-PD 15.0
Trolamine 2.0
Without oily perfume compound 1.4
Water To 100
NaLAS is C 11-15sodium alkyl benzene sulfonate.
NI (7EO) is R-(OCH 2cH 2) noH, wherein R is C 12-15alkyl, and n is 7.
SLES (3EO) is the Zetesol NL with average 3 oxyethyl groups.
Alkyl betaine is bB (from Huntsman)
With the ratio of liquid for cloth 10: 1 in Linitester, described composition is used for cleaning the mixture of white fabrics: woven cotton, micro fiber polyester, woven polyester-cotton blend and knitting nylon spandex fiber.Described fabric is equal areas.Use 26 °F of rench hard water.Each cleaning continues 20 minutes, succeeded by 2 rinsings in 75ml water.This process twice is repeated, then dry described fabric with the base composition provided in table 2 (namely without any polymkeric substance).
Then, described cleaning step is repeated 3 times again, and each cleaning now all adds dirt bar and brings simulation contaminated.Dirt band is 8.6: 1 relative to the weight ratio of white fabrics.The dirt band used is SBL 2004 Soil Ballast Fabrics (from wfk Testgewebe GmbH) and the Stanley Clay band (from WarwickEquest UK) of weight ratio 1: 1.Repeat each time for these 3 times, described composition also comprises the polymkeric substance of 3.5wt%, the corresponding minimizing in equilibrium water.Described composition all uses with 2.3g/L.
Shift out described cloth, reflectance spectrum measured by dry and use reflectometer.Measure the enhancing in cleaning by R460, described R460 is provided by following:
R460=R460 (polymkeric substance)-R460 (contrast)
Cloth is more clean, and reflectivity is higher, and therefore relative to contrast, larger R460 is the better increase of cloth degree of cleaning.Result provides in table 3.
table 3
PEI (1300) is unethoxylated PEI.
Polymer P 1 (having 1 ethoxylation chain) and P2 (having 2 ethoxylation chains) show best performance in all performances, in cotton, polyester-cotton blend and polyester have good effect, nylon elastic fiber does not have as negative effect seen large from whole non-alkoxylate PEI.
Note in the following example 2 and 4, the data for P1 and P30 are summations of the data from this test, but not repeating data.
embodiment 2
With tosylation PEG: polyethylene imine based mol ratio is 1: 1, repeat synthesis and the experiment of embodiment 1.The polyethylene glycol monomethyl ether used changes and does:
CH 3(O-CH 2cH 2) noH (Mn=750), and the gained alkoxylate PEI polymkeric substance of numbering P1-750; With
CH 3(O-CH 2cH 2) noH (Mn=2000), and the gained alkoxylate PEI polymkeric substance of numbering P1-2000.
Wash result provides in table 4.
table 4
··R 460
P1 20.1
P1-750 15.9
P1-2000 12.3
PEI (1300) (reference) 10.7
P30 (reference) 6.4
R 460the R for often kind of fabric 460summation.
P1, P1-750, and P1-2000 provides the result of the improvement with reference to polymkeric substance relative to P30 and PEI (1300).Shorter chain alkoxy PEI provides optimum result.
embodiment 3
For P1 with the content of 0.4377wt% (in washing soln 10ppm), repeat the washing experiment of embodiment 1.Result provides in table 5.
table 5
··R460
P1(10ppm) 15.9
Polymkeric substance of the present invention provides benefit at low levels.
embodiment 4
With tosylation PEG: polyethylene imine based mol ratio is 1: 1, repeat synthesis and the experiment of embodiment 1.Polyethylene imine based changing is polyethylene imine based (Mw=800) and numbering Q1.Wash result provides in table 6.
table 6
··R460
P1 20.1
Q1 15.3
embodiment 5
Table 7 is according to further detergent composition of the present invention.
table 7
Wt% (solid)
NaLAS 4.9
NI(7EO) 7.3
SLES(3EO) 2.4
Alkyl betaine 0.9
1,2-PD 15.0
Trolamine 2.0
Without oily perfume compound 1.4
P1 0.3
Lipase 0.002
Cellulase 0.002
Amylase 0.002
Acid violet 50 0.002
Fluorescent agent 0.1
Water To 100
Enzyme level is represented as true protein.The lipase used is Lipoclean tM(Novozymes); The Mierocrystalline cellulose used is Celluclean tM(Novozymes); The amylase used is Stainzyme tM(Novozymes).

Claims (11)

1. a laundry detergent composition, it comprises the detergent surfactant being selected from non-ionic type and aniorfic surfactant of 5 to 30wt%, and the poly-alkoxylation polyethyleneimine polymers of 0.05 to 4wt%, wherein this poly-oxyalkyl chain is directly connected to the nitrogen-atoms in PEI, with every bar chain, there is the end group that molecular weight is less than 100, and wherein said polymkeric substance is the poly-oxyalkyl chain comprising described end group is less than or equal to 3 PEI relative to the mol ratio of PEI, it causes 3 or less, preferably 2 or less, most preferably 1 nitrogen-atoms is attached to poly-oxyalkyl chain and wherein said PEI has at least 500, preferably 1000 to 2000, more preferably less than 1500, the Mw of even about 1300.
2. composition according to claim 1, wherein the mark of (wt% nonionic surface active agent)/(wt% aniorfic surfactant) is from 0.6 to 2.0.
3. composition according to claim 2, wherein the mark of (wt% nonionic surface active agent)/(wt% aniorfic surfactant) is from 0.90 to 1.2.
4. the composition according to any one in aforementioned claim, it is liquid.
5. the composition according to any one in claim 1-3, it is solid.
6. the composition according to any one in aforementioned claim, it also comprises perfume compound.
7. the composition according to any one in aforementioned claim, wherein said end group on poly-oxyalkyl chain is C 1-4alkyl, preferable methyl.
8. the composition according to any one in aforementioned claim, wherein said poly-alkoxylation is made up of polyethoxylated.
9. composition according to claim 8, the mean number of the ethylene oxide unit wherein in polyethoxylated PEI is from 5 to 50, preferably from 8 to 20, more preferably from 10 to 14.
10., according to composition in any one of the preceding claims wherein, it comprises ethoxylated nonionic tensio-active agent.
11. Laundry Washing Method, wherein the composition according to any one of claim 1-10 is diluted to the detergent surfactant of 0.3 to 1g/L, and 5 to 150ppm, preferably 10 arrive 80ppm, the level of poly-alkoxylation polyethyleneimine polymers, and use it for washing and comprise the combined load of other fabric that the fabric of nylon elastic fiber and at least one are selected from cotton, polyester-cotton blend and polyester.
CN201380025584.1A 2012-05-16 2013-05-14 Include the laundry detergent composition of poly-alkoxylation polyethylene imine Active CN104334707B (en)

Applications Claiming Priority (5)

Application Number Priority Date Filing Date Title
EP12168345.2 2012-05-16
EP12168345 2012-05-16
EP13152414 2013-01-23
EP13152414.2 2013-01-23
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CN107207998A (en) * 2015-02-13 2017-09-26 荷兰联合利华有限公司 Liquid laundry compositions
CN107207997A (en) * 2015-02-13 2017-09-26 荷兰联合利华有限公司 Liquid laundry compositions

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JP7155300B2 (en) 2018-06-26 2022-10-18 ザ プロクター アンド ギャンブル カンパニー liquid laundry detergent composition
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CN107207998A (en) * 2015-02-13 2017-09-26 荷兰联合利华有限公司 Liquid laundry compositions
CN107207997A (en) * 2015-02-13 2017-09-26 荷兰联合利华有限公司 Liquid laundry compositions
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CN107207998B (en) * 2015-02-13 2020-04-10 荷兰联合利华有限公司 Liquid laundry compositions

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EP2850166B1 (en) 2015-10-21
BR112014026932A2 (en) 2017-06-27
CN104334707B (en) 2017-08-22
BR112014026932B1 (en) 2021-08-31
BR112014026932A8 (en) 2021-04-13
WO2013171210A1 (en) 2013-11-21

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